Process of manufacturing starch solutions



Patented Nov. 26, 1951 UNITED STATS or icE to PROCESS OF MANUFACTURING STARCH SOLUTIONS lands, a corporation of the Netherlands Groningen, N ether- No Drawing. Application November 1, 1946, Se-

rial No. 707,321. In the Netherlands October Section 1, Public Law 690, August 8, 1946 Patent expires October 22, 1963 4 Claims. (01. ass-17.2)

S..Patent 2,246,635 contains the description of.a processof manufacturing starch products the. solutions of which when dried will produce waterHresistant layers, the said process being characterized by adding to the cold swelling starch an aldehyde, particularly formaldehyde, or a substance producing formaldehyde by decomposition, andof manufacturing'solutions of such starch products.

{EOD the manufacture of cold swelling starch a mixture of starch-or a starch derivative with a' limitcd proportion of water is heated on a rotary drum to a temperature adapted to remove the water and to gelatinize the starch or starch derivative while pressing the same to a thin layer under mechanical pressure and simultaneously drying the mass.

The patent mentioned above is based upon the discovery that, if an aldehyde, more particularly formaldehyde, is added to the mixture to be submitted to the cold swelling starch manufacturing process, no insoluble condensation products of the starch and the aldehyde will be formed as yet during the short heating period at a high temperature; This is shown by the fact that the cold swelling starch manufactured in the presence of an aldehyde has the property, of dissolving or swelling in cold water, like ordinary cold swelling starch.

Insoluble products, however, are formed when dissolving the-formaldehyde-cold swelling starch i'n water, drying the solution in the heat preferably inthe presence of a catalyst, and subsequently, heating the dried layer for some time, at a higher temperatureif necessary. By using the said starch products one may therefore obtain'in a very simple manner water resistant layers, which will constitute very valuable finishing, sizing and binding agents, or adhesive substances.

The formation of the insoluble products with formaldehyde is due, most likely, to the formation of bridges, e. g..methylene ether bridges between the starch molecules, whereby the solubility of the cold swelling starch is destroyed. I rthiscase the formaldehyde may react with two hydroxyl groups of the same and/or of different starch molecules, thus forming intramolecular and/or intermolecular bridges.

The formation of the said methylene-ether bridges is accelerated by the presence of catalysts, particularly acids. The decrease of the solubility. is a function of the proportion of formaldehyde and of the nature and the proportion of the acid, as well as of the other reaction conditions, such as the concentration and the temperature and the length of the heating period. In actual practicecommercial formaline is employed forthe manufacture of formaldehyde-cold" swelling starches according to U. S. Patent: 2,246,635. It is well known, that formaline gen-' erally contains a small quantity of acid (formic acid); The native starch itself may also have a slightly acid reaction on account of the acids.

present in the said starch, such as amylo-phos phoric vacid. It has now been found that this small proportion of acid will already cause during the cold swelling starch manufacturing process a certain degree of condensation accompanied by a reduced solubility, and, mostlikely,

with formation of methylene ether bridges. It is' true that this condensation does not proceed so far that the productobtained will no longer swell in cold water, but this will only be true as long as one does not use too large a proportion of commercial formalin. It is therefore stated inU. S. Patent 2,246,635 that as a rule not more than v 10% of formaldehyde, calculated on the starch, should be used. if it is desired to obtain preparations that will still swell in water in'a According to the present invention it is no possible to obtain even more readily dissolving,

or swelling,- products by carrying out the heating process for manufacturing the aldehyde cold swelling starch in a neutral or alkaline medium,

and-the invention accordingly has for its object a process of manufacturing aldehyde cold swelling starches 0f the character indicated, which;

consists in heating a mixture of starch with'a small proportion of water and an aldehyde capa-' ble of producing insoluble condensation products with the starch on a rotary drum at a temper-' ature adapted to remove the water and to gelatinize the starch," while pressing out the mass undermechanical pressure to a thin layer which is simultaneously dried, the said heating process being carried out in a non-acid medium.

When neutralizing the free acid present in the" commercial formaline used or both in the formaline and in the starch, it will be found that there is formed a cold swelling starch that is more readily soluble than the cold swelling starches produced without previously neutralize ingthe acid. This improved solubility is par ticularly noticeable if a larger proportion of form dehyde, e. g. 40%, calculated as pure aldehyde swelling starch produced with a smaller prop orw 5.

tion of formaldehyde.

Another advantage of the use of larger quan tities of aldehyde consists in that degraded.

starch products, such as soluble starch, may be used as starting materials for the.- cold swelling 1 0 starch process, since because of 'the high per--.. centage of aldehyde in the final product the layers produced from the cold swelling starches obtained in this way will still be sufficiently water resistant. Thus the type of starch material which can be used in the process claims includes,- starches which have been degraded ormodified; In the process according to Patent No. 2,246,635 (Moller), however, it is not possible to use degraded starches, owing to the fact that the quan- 2Q tityi of: aldehyde. to be added is limited; so that the. layers; obtained. from decomposed starch products would notbe suificiently water resistant. The degraded starch products maybe manufactured according to well known processes.

may also be. produced during. the manufaca tu'ring process of the cold swelling starch by adding: before or during the said process. chemicals degrading. the starch.

With the same. percentage of aldehyde, how-1 eyer, the water resistantproperties oi the. cold swelling starchesv generally will be the greater, the. smaller the degree. of degradation of the starch. molecule. 7

If desired: the aldehyde, e. g. formaldehyde, may be allowed to react for some. time in. an acid. medimn; on the starch. and the. reaction, mixture. subsequently neutralized or rendered alkaline, be.-. fore; the same, isv subjected to. the. cold swelling tarch. pr c ss. 40

51 1 the manufacture of; aldehyde cold swelling starches; in a neutral orany alkaline. medium ace. erd ig to. he inv ntion. one.- may apply: all-of; the measu es desc ibed in S:- Batent. 224.6; 35. Wh n; us a. lution or. the: cold. swell ng. starch products as finishing, sizing; or; bindin gen or as adhes v l t.isadvi ableto addanacia at sir. a the. onden ation. of: the; C01d. .W 1.: s tea and the-alde y e. hec talystused; qa his1 urposea s ei her; acid; r. a substance. en tin ac hen: heated: and; the rm;

when. us in; he, spec fi ati n. and; c .sis a e ndersw n-th si ens Thea id- Qatalr tmay al drhe. added o her hydeecold swelling starch in drycondition ad tageous n h s ase. a d e; at lyst n; .Q mold. w llin star h: p p r tio ta ne by nv r g. am ur of s arch and. mare l i dla nt of atalr t ac ld W starch. so tha heiatal l i i embed eaw ih he colds e' ar h. Partic s T elma... lQ1Yd w l n l hes ma 1 9: 5 2- mi'ired with. astarch. or starch. derivative which. does nptswell or dissolve incold water.,

Itis alsopossible to; add to;-the -alde hyde ,cold swelling; starches substances adapted to form with, 65 h ld h d the ic. e n l e en -hem pr cts, e. g. phenolsand the.like, ,amino com ponds, such; as; urea, thiourea," dicyandiamide; aminotriazines, e. g, melamine; and the. like-,. 'Ilhesesubstances. may .be added. to the coldyswell starch, after thelatter hasbendissohied; or. if:- two drycold. swelling. starch. preparations; are. used, tothe dry cold swe1'1in stamh containing, th', talystl Weinay also, employ the said;syn, the ic resin components separately; together with starch in the form of cold; swelling starch. In that case they may be added during orafter the cold swelling manufacturing process. If they are added before or during the cold swellingstarch manufacturing; process, so that they are em-.

' bedded within cold swelling starchparticles, it is of particular advantageqtouse melamine as the synthetic resin component, as it has been found that it possible to add melamine in very large quantities. to the moist starch without experiencing any. difficulties during the manufacturing process of the cold swelling starch in question, owing-- to the stability and to the very high melting point (3. C.) of the melamine.

In a contra-distinction from melamine, synthetic resin components, such as urea and phenol j which; have, a comparatively low melting point, will melt at the temperature at which the con version of starch into. cold swelling starch takes place. It will consequently be necessaryto limit. thefquantityof compounds of this nature to be added to. the. starch, in order to obtain. a, final; product of the. cold swelling starch manufactur r ing process: which is still. useful or suflici'entlyx soluble. The. use. of melamine, as a. synthetic;

resin component. moreaver, has; the great adyanei i 7 tage thatafter the drying of the finishingoe sizing; agent or adhesive. layerswill be obtained; which in comparison with the layers produced; from other synthetic.resincomponents areihighly resistant to water. or-to.washing;. p Instead of. adding. the ammotriazines. as. such;

one. ma also: use substances by: whichaminotrtazines may; be formedz'during the; coldswellinae .j starchprocess... One-may for-instance'startirmr d-icya'ndiamide by; which. melamine; is:' produced.

or from dicyandiamide, and: ure y. 'Qh' V meline is. produced;

As a. rule it will. be; necessary: f r: Qbtammse layers that; are thoroughlyi IGSgi'SIGafltqtQ water, to; use; l r r. amounts; o nthe ic: resin. 12 2090 tion to. the degreeof decompositionof the: starch; .manufactu .91: r

us d. as a mate al f r the aldehyde-cold swellingsta 1 .16; o ut ons of: he cold swc meastar hrrep-i arations according tg zthe: infi re acterizecr y a. hi h and p rmane t transnarencr anddonot pres n re oerad i nzor. crystal? lization phenomena. The; sglubilitsa martyr V.

cases etter ani hatoiv h or na cql aswl ilins starch s. Mareovcr 2 be.- used'f a Qua.- dresses; eye; a

f r izin a r m. thickenin aesntei s and: texti prinfinacr: indin gent? ar alt 11;. preparations 1 kind arse-re ul r. flhr iis; and nul erulentg lees j.

terials;

The products according to the invention,

ticular-lyhose containing syntheticiresin components are very'suitableafor beinguserliaszfinishs ing agents. for" textilepurposes particularly r i providingfinishing agentsfthat arevpermanent tog washing on yarns or fabricsmadeof cotton, li'rim;

wool; rayon and cellulose fibres-ormixturesmffthQ same with other fibrous-substances;

The textilema erii lft'o betreated is; dried after; t mpre at on w th he t rch olutiem s bseque lr. iide ireajheatssita hi h r pera ur e. s,..8 j 2!l-"C-);f.9 r s meminutesryin and; heating. tre tments. mayghe. ef erted; simultaneously; Theyarn, or fabricfisthfin. sabe isctssl. to hei usualfurther treatment L "In this manner one obtains finishing or ysha e h adr ntasrs, i

5 agents that are more permanent to washing than those obtained from the starch preparations formerly used.

In order to obtain special finishing or sizing effects auxiliary agents may be added to the finishing or sizing bath, such as fillers, e. g. China clay or talcum, softening agents, such as acid resistant fat emulsions, or finishing oils, water repelling agents, such as parafiin emulsions and other emulsions containing aluminum salts, without materially reducing the property of the finishing agents to resist washing.

The products according to the invention may also be used as binding agents for all kinds of pigments, which renders it possible to combine dyeing with coloured pigments and finishing in order to obtain colours that are both sun fast and permanent to washing. Brilliant rayon may be delustered in the same manner, while it is also possible to obtain a matting efiect that is permanent to Washing by locally applying the starch paste containing pigments by printing processes.

The invention may also be used for finishing the backside of plush and rugs (velvet and similar fabrics) in order to produce finishes which are proof against washing and will permanently fix the pile. The invention may also be used for the purpose of improving the resistance of fabrics against abrasion and wear and tear, particularly those made from cellulose staple fibre (especially when wet), whereby a general improvement of the quality is obtained.

,Finally the products according to the invention, particularly those made of decomposed starch, may be used as water proof adhesives e. g. in the manufacture of three-ply or multi-ply wood and for producing finishes which do not affect the designs on dyed or printed fabrics.

The invention will be explained by the following examples.

Example I 500 to 1000 parts by volume of commercial formalin (40% by volume) are neutralized with dilute caustic soda and diluted to a volume of 1500 parts with water containing 6 parts by weight of dissolved anhydrous sodium carbonate. 1000 parts by weight of potato starch are suspended in the solution thus obtained and the mixture is immediately converted into cold swelling starch in the usual manner.

The suspension of starch in formalin may also be left to itself for some time at a normal or a slightly raised temperature, so that the formaldehyde may be able" to react with the starch for some time, before the mixture is submitted to the cold swelling starch process. The starch will gradually dissolve completely to a very tough, transparent mass.

The same phenomenon will occur much more quickly, if a small quantity of a caustic soda solution is added instead of a small quantity of sodium carbonate. The rate of speed at which starch will swell or dissolve in a formaldehyde solution depends, apart from the temperature, on

, the pH and on the concentration of the formaldehyde.

The cold swelling starch preparations prepared according to this example contain from 10 to 20% of formaldehyde calculated on the air dry final product. By varying the proportions of the components and the reaction conditions it is, however, also possible to manufacture cold swelling starch preparations containing more than 20% of formaldehyde.

' there are dissolved 3 parts by "weight of anhy-'f drous sodium carbonate. The mixture is con'- verted into cold swelling starch in the usual man-" ner.

, Example III Example IV V 1 kg. of the paraformaldehyde cold swelling starch obtained according to Example If is intimately mixed with 100 grams of urea or with 75. grams of melamine. 60 grams of the dry mixture are stirred with 500 cm. of cold water.. The paste is left to itself for some time, after which a mixture of 420 cm. of water and 20 cm. of an solution of acetic acid is added. The whole is in-';

timately mixed by vigorous stirring. A cotton fabric is impregnated with the paste thus ob-L tained. The excess of finishing bath is removed by pressing; the fabric is dried and the condensa t1on of the urea, or of the melamine with the formaldehyde-cold swelling starch is eiiected or completed by heating the fabric at a higher tem perature, e. g. bU-ulu" C., for some minutes.

Ev en by repeated mechanical washing at 70-80 C. with a solution containing 5 grams of soap and] 3 grams of soda per liter the finish will remain in the fabric.

Emample V 70 parts by weight of comminuted melamine are intimately mixed with parts by volume of water and subsequently diluted with a solution of: 3 parts by weight of NazCOs in 650 parts by vol-1'. ume of water. 500 parts by weight of potato starch are suspended in this mixture and the suspension thus obtained is converted into cold swelling starch in the usual manner. 250 parts by weight of the melamine cold swelling starch obtained in this manner are intimately mixed in dry condition with 250 parts by weight of the formaldehyde cold swelling starch, obtained according to Example I. This mixture may be converted with a tenor fifteenfold quantity of cold water into a finishing paste by means of which after the addition of a catalyst one obtains finishes that are permanent to washing.

Example VI A mixture of 5.7 parts by weight of formaldehyde cold swelling starch containing 16% of formaldehyde content and 1% parts by weight of a melamine cold swelling starch containing 21% of melamine is dissolved in 57.6 parts by volume of cold water. This solution is intimately mixed with a mixture of 6 parts by Weight of talcum and 6 parts by weight of China clay, the said mixture having previously been boiled with 12 parts by volume of water. The mass is diluted arrest-as.

while stirring with 28.4 partsby volume of water towhich there have beenadded 2 parts by volumeof an acetic acid solution of 80%. A cotton fabric is treated with the solution thus obtained, in, the, same manner as in Example IV. After or during the, drying treatment the finished fabric isheated at 120 C. during some minutes.

The fillers and stiffening agents are practically not removed even after repeated washings in the manner described in Example IV.

? Example VII 1.0.0 parts by weight of dicyandiamide and 1000 v parts by weight of potato starch are suspended in a mixture of'700 parts by volume of water and 300. parts by 'volume of 1 N caustic soda. The suspension is submitted to the cold swelling starch process at a. temperature of about 170 C. There is obtained, a melamine'containing, cold swelling starch preparation that will readily dissolve in coldiwater and that in combination with a form-' aldehyde-cold swelling starch obtained according to Example I may be used for producing washproof finishes on fabrics.

Eccample- VIII cold swelling starches, which comprises, impart'-' ing to a, mixture of a starchy material "of the group consisting of starch and soluble starches,

and an aqueous solution of commercial formaldehyde in a proportion of, at least, 20%, calcu lated' as pure formaldehyde on air dry sta rchia pH of at least '7 by adding an alkaline substance and heating the mixture on a rotary drum to a temperature adapted to removethe water and to gelatinizethe starchymaterial, w-hilepressing out the. mass under mec'hanica-l pressure to'a thin layer which is simultaneously dried,

2. A dry stable starch preparation, soluble cold; water which. comprises a. mixture of the;

product of claim 1 and separate particles-of a substance, taken from a group consistingof phenols, urea and amino; triazines, capable of reacting with formaldehyde, so as to form synthetic resin-like condensation products.

3..A process of manufacturing formaldehyde coldswelling; starches, which comprises, impart ingto a mixture of a starchy material of the group consisting of starch and soluble starches, and an 7 aqueous solutionof commercial formaldehyde in aproportion of at least, 40%, calculated as pure formaldehydeon air, 'dry starch, a pH, of at least 7, by addingan alkaline substance and heating the mixture ona rotary drum to a temperature adapted to remove the water and to gelatinize-the starchy material, while pressing out the mass under mechanical pressure to a thin layer which is simultaneously- 7 dried.

4.,A dry stable starch preparation, solubleiin: cold "water which comprises a mixture of the product of claim 3 and separate particles of a substancetaken. from a group consisting of phenols, urea and-amino triazines, capable ,of react:- ing, with formaldehyde, so as to form synthetic resin-like condensation products.

JAN LOLKEMAJ v WILLEMALBERTUS VAN DER'MEER'. j

REFERENCES CITED The following references areof record in the file of this patent:

UNITED STATES PATENTS,

Date

Number Name I 2,246,635 Moller June 24, 1941- 2,275,314 Pierson" Mar. 3', 1942 2,302,310 Glarum Nov. 17; 1942 2,399,489 Landes Apr. 30, 1946 FOREIGN PATENTS Number Country Date Great Britain May 31,1939

oTHER REFERENCES Blanksma Recuiel des travaux chimiques; des; Pays-:Baa vol. 4 411 385 351-360 (1929) 233.3. 

1. A PROCESS OF MANUFACTURING FORMALDEHYDE COLD SWELLING STARCHES, WHICH COMPRISES, IMPARTING TO A MIXTURE OF A STARCHY MATERIAL OF THE GROUP CONSISTING OF STARCH AND SOLUBLE STARCHESM AND AN AQUEOUS SOLUTION OF COMMERICAL FORMALDEHYDE IN A PROPORTION OF AT LEAST 20%, CALCULATED AS PURE FORMALDEHYDE ON AIR DRY STARCH, A PH OF AT LEAST 7, BY ADDING AN ALKALINE SUBSTANCE AND HEATING THE MIXTURE ON A ROTARY DRUM TO A TEMPERATURE ADAPTED TO REMOVE THE WATER AND TO GELATINIZE THE STARCHY MATERIAL, WHILE PRESSING OUT THE MASS UNDER MECHANICAL PRESSURE TO A THIN LAYER WHICH IS SIMULTANEOUSLY DRIED. 